Walking for the daily commute is one potential strategy for increasing physical activity levels. Understanding the behaviour-specific environmental correlates associated with commuter walking will help effective interventions to be identified and developed. The aim of this study was to examine the associations of perceptions of the environment in the workplace ‘neighbourhood’ and commuter walking. Participants in the baseline survey of the Walking Works intervention study reported perceptions of ten environmental attributes in their workplace neighbourhood, availability of public transport, time spent walking to and from work in the last seven days, their participation in physical activity and socio-demographic characteristics (n=676). We built a series of multivariate logistic regression models to examine associations between each environmental item, public transport availability and commuter walking. Half (52%) of respondents were classified as commuter walkers (n=352) (66% female; 47% aged <30 years). Respondents were significantly more likely to walk for their daily commute if they reported there to be convenient walking routes (OR (odds ratio) 2.05, 95% CI (confidence interval) 1.23–3.42), suitable pavements (OR 2.23, 95% CI 1.23–4.04), maintained pavements (OR 1.64, 95% CI 1.02–2.62) or convenient public transport (OR 4.98, 95% CI 3.34–7.44) after adjusting for socio-demographic characteristics, free car parking at work and distance lived from work. Creating ‘pedestrian friendly’ environments in workplace surroundings may be important for encouraging walking for the daily commute to work. Such environments would include convenient routes, suitable and maintained pedestrian infrastructure and convenient access to public transport. Improving and maintaining the walking environment around existing workplaces and ensuring infrastructure around new workplaces is designed to support commuter walking should be considered a priority area for investment.